CN110773227A - Walnut shell powder acid-base functionalized catalyst, preparation method and application - Google Patents
Walnut shell powder acid-base functionalized catalyst, preparation method and application Download PDFInfo
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- CN110773227A CN110773227A CN201911011210.XA CN201911011210A CN110773227A CN 110773227 A CN110773227 A CN 110773227A CN 201911011210 A CN201911011210 A CN 201911011210A CN 110773227 A CN110773227 A CN 110773227A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
The invention discloses a walnut shell powder acid-base functionalized catalyst, a preparation method and application thereof, and the catalyst comprises an amino functionalized alkaline walnut shell powder-based catalyst WSO-NH
2Sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3The catalyst prepared by mixing H has the advantages of low price, wide source, reproducibility and biodegradability. The method firstly prepares the catalyst, and then utilizes the catalyst to synthesize the aromatic aldehyde dimethyl acetal and the malononitrile in an efficient and green way by taking the aromatic aldehyde dimethyl acetal and the malononitrile as the initial raw materials in a one-pot two-step serial Knoevenagel reaction modeThe corresponding α -unsaturated compound was obtained in a yield of up to 97%.
Description
Technical Field
The invention belongs to the technical field of natural polymer modification and organic catalytic synthesis, and relates to a walnut shell powder acid-base functionalized catalyst, a preparation method and application.
Background
In organic synthesis, Knoevenagel condensation reaction is an important reaction for synthesizing α -unsaturated compounds and forming C ═ C, specifically, refers to a condensation reaction of aldehyde carbonyl and ketone carbonyl with active methylene, and the reaction is widely applied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a walnut shell powder acid-base functionalized catalyst, a preparation method and application, and solves the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a walnut shell powder acid-base functionalized catalyst, which comprises an amino functionalized alkaline walnut shell powder-based catalyst WSO-NH
2Sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H, the mass ratio of the two is 1: 1.
The alkaline walnut shell powder-based catalyst WSO-NH
2Structural formula (II)Is composed of
The acidic walnut shell powder-based catalyst WSO-SO
3H has a structural formula of
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the catalyst for acid-base functionalization of walnut shell powder is provided, and comprises the following steps:
1) preparation of WSO: mixing walnut shell powder, NaOH and water, adding epichlorohydrin, and heating at 80 deg.C under N
2Reacting for 3 hours in the environment, sequentially centrifuging the obtained product, adding water into the product, and performing suction filtration, washing and drying to obtain a product, namely the epoxidized walnut shell WSO;
2)WSO-NH
2the preparation of (1): mixing the product WSO obtained in the step 1) with NaOH and water, standing at room temperature for 1 hour, adding triethylene tetramine, and adding N at 50 DEG C
2After 24 hours of reaction in the environment, carrying out suction filtration, washing and drying to obtain a product, namely the amido functionalized alkaline walnut shell powder-based catalyst WSO-NH
2；
3)WSO-SO
3H, preparation: the product WSO-NH of the step 2)
2And CH
2Cl
2Mixing, and dropwise adding HSO under ice-water bath condition
3Cl, reacting for 6 hours, filtering, washing and drying to obtain a product, namely the sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H。
In a preferred embodiment of the present invention, in the step 1), the using ratio of the walnut shell powder, NaOH, water and epichlorohydrin is 4.8-5.2 g: 4.2-4.3 g: 20-25 mL: 9.6-10.0 g.
In a preferred embodiment of the present invention, in the step 2), the ratio of the WSO, NaOH, water and triethylene tetramine is 3.8-4.2 g: 10-12 g: 5-6 mL: 3.8-4.2 mL.
In the inventionIn a preferred embodiment, in the step 3), WSO-NH is performed
2、CH
2Cl
2And HSO
3The dosage ratio of Cl is 1.8-2.2 g: 20-25 mL: 1.8-2.2 mL.
The third technical scheme adopted by the invention for solving the technical problems is to provide the application of the walnut shell powder acid-base functionalized catalyst, which is used for catalyzing one-pot two-step tandem Knoevenagel reaction between aromatic aldehyde dimethyl acetal and malononitrile to prepare α -unsaturated compounds.
In a preferred embodiment of the present invention, the application comprises the steps of:
1) mixing aromatic aldehyde dimethyl acetal, malononitrile, water and a catalyst, wherein the catalyst comprises WSO-NH with the mass ratio of 1:1
2And WSO-SO
3H are sequentially placed in reaction bottles;
2) placing the reaction bottle in a microwave reactor, starting a magnetic stirring device, and carrying out two-step serial Knoevenagel reaction at 70 ℃ for 5-10 minutes in a one-pot manner under the microwave radiation condition with the power of 300W;
3) after the reaction is finished, adding ethyl acetate into the reaction bottle, dissolving the product into the ethyl acetate to obtain a reaction mixed solution, performing centrifugal separation on the reaction mixed solution at a rotating speed of not less than 4000 revolutions, and performing centrifugal separation to obtain solid residue, namely WSO-NH
2、WSO-SO
3H。
4) Carrying out reduced pressure rotary evaporation on the upper layer organic phase after centrifugal separation to obtain α -unsaturated compound crude product, recrystallizing and purifying by using ethanol solvent to finally obtain a pure target product, wherein the structural formula of the target product is shown in the specification
In a preferred embodiment of the invention, the aromatic aldehyde dimethyl acetal, malononitrile, water, WSO-NH
2、WSO-SO
3The dosage ratio of H is 2.4-2.5 mmol: 2.5-2.6mmol:0.8-1.0mL：100mg：100mg。
In a preferred embodiment of the present invention, the aromatic aldehyde dimethyl acetal has the structural formula
In a preferred embodiment of the invention, the malononitrile has the formula
Compared with the background technology, the technical scheme has the following advantages:
the catalyst prepared by the invention is renewable and degradable, has the advantages of high catalytic activity (complete reaction can be achieved within 5-10 minutes), high yield (97 percent) and the like in the reaction of preparing α -unsaturated compounds by one-pot two-step Knoevenagel reaction, and is cheap and easy to obtain and has little corrosion to production equipment.
The invention adopts aromatic aldehyde dimethyl acetal to replace aromatic aldehyde in the traditional reaction system, and adopts a reproducible and degradable walnut shell powder acid-base functionalized catalyst WSO-NH
2、WSO-SO
3Compared with the reported reaction system which takes the aromatic aldehyde and the malononitrile as raw materials and takes organic primary amine or secondary amine as a catalyst, the reaction system has the defects of low reaction activity, need of using toxic organic solvents, long reaction time and the like.
Drawings
FIG. 1 shows WSO-NH
2And WSO-SO
3The structural formula of H.
FIG. 2 is a synthetic route for the catalyst of the present invention.
Detailed Description
Example 1
The acid-base functionalized catalyst for walnut shell powder comprises an amino functionalized alkaline walnut shell powder-based catalyst WSO-NH
2Sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H, the mass ratio of the two is 1: 1.
Fig. 2 is a synthesis route of a walnut shell powder acid-base functionalized catalyst in this embodiment, and the specific preparation method includes the following steps:
1) preparation of WSO: adding 5.0g walnut shell powder, 4.25g NaOH, 25mL water into 100mL flask, adding 10.0g epichlorohydrin, and heating at 80 deg.C under N
2Reacting for 3 hours in the environment, sequentially centrifuging the obtained product, adding water into the product, and performing suction filtration, washing and drying to obtain a product, namely the epoxidized walnut shell WSO;
2)WSO-NH
2the preparation of (1): 4.0g of WSO, 12g of NaOH and 6.0mL of water were mixed, placed in a flask and left at room temperature for 1 hour, and 4.0mL of triethylenetetramine was added thereto, and N was added at 50 ℃
2After 24 hours of reaction in the environment, carrying out suction filtration, washing and drying to obtain a product, namely the amido functionalized alkaline walnut shell powder-based catalyst WSO-NH
2；
3)WSO-SO
3H, preparation: 2.0g of WSO-NH
2And 25.0mL CH
2Cl
2Adding into a round-bottom flask, and dropwise adding 2.0mL HSO under the condition of ice-water bath
3Cl, reacting for 6 hours, filtering, washing and drying to obtain a product, namely the sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H。
WSO-NH prepared in this example
2And WSO-SO
3H is shown in FIG. 1.
Example 2
Using the catalyst prepared in example 1, α -unsaturated compound III was prepared, having the following structural formula:
the method comprises the following specific steps:
1) benzaldehyde dimethyl acetal (2.4mmol), malononitrile (2.6mmol), water (1.0mL) and walnut shell powder acid-base functionalized catalyst WSO-NH
2(100mg)、WSO-SO
3H (100mg) was placed in the reaction flask in turn.
2) The reaction flask is placed in a microwave reactor, and the reaction time, temperature and microwave radiation power are set. Starting the microwave reactor, starting the magnetic stirring device, and reacting for 10 minutes under the conditions that the reaction temperature is 70 ℃ and the microwave power is 300W.
3) Monitoring the reaction by thin layer chromatography, adding ethyl acetate into a reaction bottle after the reaction is finished, dissolving the product in ethyl acetate, performing high-speed centrifugal separation on the reaction mixed solution, and performing centrifugal separation to obtain solid residue walnut shell powder acid-base catalyst WSO-NH
2、WSO-SO
3H。
4) And (3) carrying out reduced pressure rotary evaporation on the upper layer organic phase to obtain α -unsaturated compound crude product, and further carrying out recrystallization purification to obtain 0.36g of target product pure product with the yield of 97%.
Compared with the traditional route for preparing the compound, the method has the advantages of green and efficient catalyst, low price, easy obtainment, reproducibility, degradability, water as a solvent, short reaction time, no need of separating an intermediate, high yield and the like. The melting point, infrared and nuclear magnetic characterization of the compound is as follows: m.p.84.0 ℃; FT-IR (KBr, cm)
-1):3032,2920,2222,1589,1566,1491,1449,1265,1271,1100；
1H NMR(500MHz,CDCl
3)δ:7.94(d,J＝7.3Hz,2H),7.81(s,1H),7.66(t,J＝7.5Hz,1H),7.57(t,J＝8.3Hz,2H)。
Example 3
Example 3 differs from example 2 in α -preparation of unsaturated compound IV (structural formula:
the preparation method comprises the following steps: m-bromobenzaldehyde dimethyl acetal (2.4mmol), malononitrile (2.6mmol), water (1.0mL) and walnut shellsPowder acid-base functionalized catalyst WSO-NH
2(100mg)、WSO-SO
3H (100mg) is sequentially placed in a reaction bottle, the reaction is carried out for 10 minutes under the conditions that the reaction temperature is 70 ℃ and the microwave power is 300W, the reaction is monitored by a thin layer chromatography technology, after the reaction is finished, the generated liquid is subjected to rotary evaporation operation to obtain a crude product, then 0.49g of a target product α -unsaturated compound IV is obtained by ethanol recrystallization and drying, and the yield is 89%.
Compared with the traditional route for preparing the compound, the method has the advantages of green and efficient catalyst, low price, easy obtainment, reproducibility, degradability, water as a solvent, short reaction time, no need of separating an intermediate, high yield and the like. The melting point, infrared and nuclear magnetic characterization of the compound is as follows: m.p.109.1-110.1 deg.C; FT-IR (KBr, cm)
-1):3031,2919,2230,1591,1566,1476,1413；
1H NMR(500MHz,CDCl
3)δ:7.99(s,1H),7.92(d,J＝7.9Hz,1H),7.78(d,J＝8.0Hz,1H),7.73(s,1H),7.45(t,J＝8.0Hz,1H)。
Example 4
Example 4 differs from example 2 in α -preparation of unsaturated compound V (formula:
the preparation method comprises the following steps: o-bromobenzaldehyde dimethyl acetal (2.4mmol), malononitrile (2.6mmol), water (1.0mL) and walnut shell powder acid-base functionalized catalyst WSO-NH
2(100mg)、WSO-SO
3H (100mg) is sequentially placed in a reaction bottle, the reaction is carried out for 10 minutes under the conditions that the reaction temperature is 70 ℃ and the microwave power is 300W, the reaction is monitored by a thin layer chromatography technology, after the reaction is finished, the generated liquid is subjected to rotary evaporation operation to obtain a crude product, then 0.53g of a target product α -unsaturated compound V is obtained by ethanol recrystallization and drying, and the yield is 95%.
Compared with the traditional route for preparing the compound, the method has the advantages of green and efficient catalyst, low price, easy obtainment, reproducibility, degradability, water as a solvent, short reaction time, no need of separating an intermediate, high yield and the like. The combination ofMelting point, infrared and nuclear magnetic characterization of the compounds were as follows: m.p.90.3-91.0 deg.c; FT-IR (KBr, cm)
-1):3043,2922,2231,1584,1560,1460,1437；
1H NMR(500MHz,CDCl
3)δ:8.24(s,1H),8.15(d,J＝7.7Hz,1H),7.77(d,J＝7.8Hz,1H),7.53-7.47(m,2H)。
Example 5
Example 5 differs from example 2 in α -preparation of the unsaturated compound VI (formula:
the preparation method comprises the following steps: p-bromobenzaldehyde dimethyl acetal (2.4mmol), malononitrile (2.6mmol), water (1.0mL) and walnut shell powder acid-base functionalized catalyst WSO-NH
2(100mg)、WSO-SO
3H (100mg) is sequentially placed in a reaction bottle, the reaction is carried out for 10 minutes under the conditions that the reaction temperature is 70 ℃ and the microwave power is 300W, the reaction is monitored by a thin layer chromatography technology, after the reaction is finished, the generated liquid is subjected to rotary evaporation operation to obtain a crude product, then 0.49g of a target product α -unsaturated compound VI is obtained by ethanol recrystallization and drying, and the yield is 88%.
Compared with the traditional route for preparing the compound, the method has the advantages of green and efficient catalyst, low price, easy obtainment, reproducibility, degradability, water as a solvent, short reaction time, no need of separating an intermediate, high yield and the like. The melting point, infrared and nuclear magnetic characterization of the compound is as follows: m.p.159.6-160.4 ℃; FT-IR (KBr, cm)
-1):3032,2918,2225,1581,1553,1488,1407；
1H NMR(500MHz,CDCl
3)δ:7.80(d,J＝8.5Hz,2H),7.75(s,1H),7.71(d,J＝8.6Hz,2H)。
Example 6
Example 6 differs from example 2 in α -preparation of unsaturated compound VII (formula:
the preparation method comprises the following steps: 4-methoxybenzaldehyde dimethyl acetal (2.4 mm)ol), malononitrile (2.6mmol), water (1.0mL) and walnut shell powder acid-base functionalized catalyst WSO-NH
2(100mg)、WSO-SO
3H (100mg) is sequentially placed in a reaction bottle, the reaction is carried out for 5 minutes under the conditions that the reaction temperature is 70 ℃ and the microwave power is 300W, the reaction is monitored by a thin layer chromatography technology, after the reaction is finished, the generated liquid is subjected to rotary evaporation operation to obtain a crude product, then 0.43g of a target product α -unsaturated compound VI is obtained by ethanol recrystallization and drying, and the yield is 96%.
Compared with the traditional route for preparing the compound, the method has the advantages of green and efficient catalyst, low price, easy obtainment, reproducibility, degradability, water as a solvent, short reaction time, no need of separating an intermediate, high yield and the like. The melting point, infrared and nuclear magnetic characterization of the compound is as follows: m.p.115.1-116.6 deg.C; FT-IR (KBr, cm)
-1):3027,2918,2221,1604,1570,1512,1427；
1H NMR(500MHz,CDCl
3):δ:7.93(d,J＝8.9Hz,2H),7.67(s,1H),7.03(d,J＝8.7Hz,2H),3.93(s,3H)。
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. The acid-base functionalized catalyst for walnut shell powder is characterized in that: comprises an amino functionalized alkaline walnut shell powder-based catalyst WSO-NH
2Sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H, the mass ratio of the two is 1: 1.
2. The walnut shell powder acid-base functionalized catalyst according to claim 1, characterized in that:
the alkaline walnut shell powder-based catalyst WSO-NH
2Has the structural formula
The acid nucleusPeach shell powder-based catalyst WSO-SO
3H has a structural formula of
3. A preparation method of a walnut shell powder acid-base functionalized catalyst is characterized by comprising the following steps:
1) preparation of WSO: mixing walnut shell powder, NaOH and water, adding epichlorohydrin, and heating at 80 deg.C under N
2Reacting for 3 hours in the environment, sequentially centrifuging the obtained product, adding water into the product, and performing suction filtration, washing and drying to obtain a product, namely the epoxidized walnut shell WSO;
2)WSO-NH
2the preparation of (1): mixing the product WSO obtained in the step 1) with NaOH and water, standing at room temperature for 1 hour, adding triethylene tetramine, and adding N at 50 DEG C
2After 24 hours of reaction in the environment, carrying out suction filtration, washing and drying to obtain a product, namely the amido functionalized alkaline walnut shell powder-based catalyst WSO-NH
2；
3)WSO-SO
3H, preparation: the product WSO-NH of the step 2)
2And CH
2Cl
2Mixing, and dropwise adding HSO under ice-water bath condition
3Cl, reacting for 6 hours, filtering, washing and drying to obtain a product, namely the sulfonic acid functionalized acidic walnut shell powder-based catalyst WSO-SO
3H。
4. The method for preparing the catalyst for acid-base functionalization of walnut shell powder according to claim 3, is characterized in that: in the step 1), the using amount ratio of the walnut shell powder, NaOH, water and epichlorohydrin is 4.8-5.2 g: 4.2-4.3 g: 20-25 mL: 9.6-10.0 g.
5. The method for preparing the catalyst for acid-base functionalization of walnut shell powder according to claim 3, is characterized in that: in the step 2), the dosage ratio of WSO, NaOH, water and triethylene tetramine is 3.8-4.2 g: 10-12 g: 5-6 mL: 3.8-4.2 mL.
6. The method for preparing the catalyst for acid-base functionalization of walnut shell powder according to claim 3, is characterized in that: in the step 3), WSO-NH
2、CH
2Cl
2And HSO
3The dosage ratio of Cl is 1.8-2.2 g: 20-25 mL: 1.8-2.2 mL.
7. The application of the catalyst for acid-base functionalization of walnut shell powder, which is disclosed by any one of claims 1-2, is characterized in that the catalyst is used for catalyzing one-pot two-step tandem Knoevenagel reaction between aromatic aldehyde dimethyl acetal and malononitrile to prepare α -unsaturated compounds.
8. The application of the walnut shell powder acid-base functionalized catalyst according to claim 7 is characterized by comprising the following steps:
1) mixing aromatic aldehyde dimethyl acetal, malononitrile, water and a catalyst, wherein the catalyst comprises WSO-NH with the mass ratio of 1:1
2And WSO-SO
3H are sequentially placed in reaction bottles;
2) placing the reaction bottle in a microwave reactor, starting a magnetic stirring device, and carrying out two-step serial Knoevenagel reaction at 70 ℃ for 5-10 minutes in a one-pot manner under the microwave radiation condition with the power of 300W;
3) after the reaction is finished, adding ethyl acetate into the reaction bottle, dissolving the product into the ethyl acetate to obtain a reaction mixed solution, performing centrifugal separation on the reaction mixed solution at a rotating speed of not less than 4000 revolutions, and performing centrifugal separation to obtain solid residue, namely WSO-NH
2、WSO-SO
3H。
4) Carrying out reduced pressure rotary evaporation on the upper layer organic phase after centrifugal separation to obtain α -unsaturated compound crude product, recrystallizing and purifying by using ethanol solvent to finally obtain a pure target product, wherein the structural formula of the target product is shown in the specification
9. The application of the walnut shell powder acid-base functionalized catalyst according to claim 8 is characterized in that: the aromatic aldehyde dimethyl acetal, malononitrile, water and WSO-NH
2、WSO-SO
3The dosage ratio of H is 2.4-2.5 mmol: 2.5-2.6mmol, 0.8-1.0 mL: 100 mg: 100 mg.
10. The application of the walnut shell powder acid-base functionalized catalyst according to claim 8 is characterized in that: the structural formula of the aromatic aldehyde dimethyl acetal is any one of the following formulas
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013158740A (en) * | 2012-02-07 | 2013-08-19 | Nippon Shokubai Co Ltd | Manufacturing method using acid-base catalyst, and acid-base catalyst |
| CN103381357A (en) * | 2013-07-30 | 2013-11-06 | 河海大学 | Preparation method for modified walnut shell cation adsorbent |
| CN108435248A (en) * | 2018-03-13 | 2018-08-24 | 西北师范大学 | A kind of preparation and application of the composite magnetic catalyst of magnetic retention sulfonic acid load amine-based catalysts |
| CN110252400A (en) * | 2019-06-21 | 2019-09-20 | 华侨大学 | A kind of preparation method of walnut shell graft beta-cyclodextrin type catalyst and 2- Amino 3 cyano -4H- pyran derivate |
-
2019
- 2019-10-23 CN CN201911011210.XA patent/CN110773227A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013158740A (en) * | 2012-02-07 | 2013-08-19 | Nippon Shokubai Co Ltd | Manufacturing method using acid-base catalyst, and acid-base catalyst |
| CN103381357A (en) * | 2013-07-30 | 2013-11-06 | 河海大学 | Preparation method for modified walnut shell cation adsorbent |
| CN108435248A (en) * | 2018-03-13 | 2018-08-24 | 西北师范大学 | A kind of preparation and application of the composite magnetic catalyst of magnetic retention sulfonic acid load amine-based catalysts |
| CN110252400A (en) * | 2019-06-21 | 2019-09-20 | 华侨大学 | A kind of preparation method of walnut shell graft beta-cyclodextrin type catalyst and 2- Amino 3 cyano -4H- pyran derivate |
Non-Patent Citations (1)
| Title |
|---|
| PILLAIYAR PUTHIARAJ等: "Dual-functionalized porous organic polymer as reusable catalyst for one-pot cascade C-C bond-forming reactions", 《MOLECULAR CATALYSIS》 * |
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Application publication date: 20200211 |